Catalyst modifiers and their use in the polymerization of olefin(s)

ABSTRACT

The present invention relates to the use of at least one acid and at least one base and/or at least one reductant and at least one oxidant that when used with a polymerization catalyst in a polymerization process results in the controllable generation of a catalyst inhibitor that renders the polymerization catalyst substantially or completely inactive.

RELATED APPLICATION DATA

This application is a Divisional of U.S. patent application, Ser. No.09/392,421, filed Sep. 9, 1999, now issued as U.S. Pat, No. 6,346,584.

FIELD OF THE INVENTION

The present invention relates to a method for improving operability in aprocess for polymerizing olefin(s). In particular, the invention isdirected to a method for controlling the kinetics of an olefinpolymerization catalyst.

BACKGROUND OF THE INVENTION

Advances in polymerization and catalysis have resulted in the capabilityto produce many new polymers having improved physical and chemicalproperties useful in a wide variety of superior products andapplications. With the development of new catalysts the choice ofpolymerization-type (solution, slurry, high pressure or gas phase) forproducing a particular polymer has been greatly expanded. Also, advancesin polymerization technology have provided more efficient, highlyproductive and economically enhanced processes.

Especially illustrative of these advances is the development oftechnology utilizing bulky ligand metallocene-type catalyst systems.Regardless of these technological advances in the polyolefin industry,common problems, as well as new challenges associated with processoperability still exist. For instance, the tendency for a gas phase orslurry phase process to foul and/or sheet remains a challenge using anyolefin polymerization catalyst.

For example, in a continuous slurry process fouling on the walls of thereactor, which act as a heat transfer surface, can result in manyoperability problems. Poor heat transfer during polymerization canresult in polymer particles adhering to the walls of the reactor. Thesepolymer particles can continue to polymerize on the walls and can resultin a premature reactor shutdown. Also, depending on the reactorconditions, some of the polymer may dissolve in the reactor diluent andredeposit on for example the metal heat exchanger surfaces.

In a typical continuous gas phase process, a recycle system is employedfor many reasons including the removal of heat generated in the processby the polymerization. Fouling, sheeting and/or static generation in acontinuous gas phase process can lead to the ineffective operation ofvarious reactor systems. For example, the cooling mechanism of therecycle system, the temperature probes utilized for process control andthe distributor plate, if affected, can lead to an early reactorshutdown.

Evidence of, and solutions to, various process operability problems havebeen addressed by many in the art. For example, U.S. Pat. Nos.4,792,592, 4,803,251, 4,855,370 and 5,391,657 all discuss techniques forreducing static generation in a polymerization process by introducing tothe process for example, water, alcohols, ketones, and/or inorganicchemical additives; European Patent EP 0 634 421 B1 discussesintroducing directly into the polymerization process water, alcohol andketones to reduce fouling. A PCT publication WO 97/14721 published Apr.24, 1997 discusses the suppression of fines that can cause sheeting byadding an inert hydrocarbon to the reactor; U.S. Pat. No. 5,627,243discusses a new type of distributor plate for use in fluidized bed gasphase reactors; PCT publication WO 96/08520 discusses avoiding theintroduction of a scavenger into the reactor; U.S. Pat. No. 5,461,123discusses using sound waves to reduce sheeting; U.S. Pat. No. 5,066,736and EP-A1 0 549 252 discuss the introduction of an activity retarder tothe reactor to reduce agglomerates; U.S. Pat. No. 5,610,244 relates tofeeding make-up monomer directly into the reactor above the bed to avoidfouling and improve polymer quality; U.S. Pat. No. 5,126,414 discussesincluding an oligomer removal system for reducing distributor platefouling and providing for polymers free of gels; EP-A1 0 453 116published Oct. 23, 1991 discusses the introduction of antistatic agentsto the reactor for reducing the amount of sheets and agglomerates; U.S.Pat. No. 4,012,574 discusses adding a surface-active compound, aperfluorocarbon group, to the reactor to reduce fouling; U.S. Pat. No.5,026,795 discusses the addition of an antistatic agent with a liquidcarrier to the polymerization zone in the reactor; U.S. Pat. No.5,410,002 discusses using a conventional Ziegler-Nattatitanium/magnesium supported catalyst system where a selection ofantistatic agents are added directly to the reactor to reduce fouling;U.S. Pat. Nos. 5,034,480 and 5,034,481 discuss a reaction product of aconventional Ziegler-Natta titanium catalyst with an antistat to produceultrahigh molecular weight ethylene polymers; U.S. Pat. No. 3,082,198discusses introducing an amount of a carboxylic acid dependent on thequantity of water in a process for polymerizing ethylene using atitanium/aluminum organometallic catalysts in a hydrocarbon liquidmedium; and U.S. Pat. No. 3,919,185 describes a slurry process using anonpolar hydrocarbon diluent using a conventional Ziegler-Natta-type orPhillips-type catalyst and a polyvalent metal salt of an organic acid.

There are various other known methods for improving operabilityincluding coating the polymerization equipment, for example, treatingthe walls of a reactor using chromium compounds as described in U.S.Pat. Nos. 4,532,311 and 4,876,320; injecting various agents into theprocess, for example PCT Publication WO 97/46599 published Dec. 11, 1997discusses feeding into a lean zone in a polymerization reactor anunsupported, soluble metallocene-type catalyst system and injectingantifoulants or antistatic agents into the reactor; controlling thepolymerization rate, particularly on start-up; and reconfiguring thereactor design.

Others in the art to improve process operability have discussedmodifying the catalyst system by preparing the catalyst system indifferent ways. For example, methods in the art include combining thecatalyst system components in a particular order; manipulating the ratioof the various catalyst system components; varying the contact timeand/or temperature when combining the components of a catalyst system;or simply adding various compounds to the catalyst system. Thesetechniques or combinations thereof are discussed in the literature.Especially illustrative in the art is the preparation procedures andmethods for producing bulky ligand metallocene-type catalyst systems,more particularly supported bulky ligand metallocene-type catalystsystems with reduced tendencies for fouling and better operability.Examples of these include: WO 96/11961 published Apr. 26, 1996 discussesas a component of a supported catalyst system an antistatic agent forreducing fouling and sheeting in a gas, slurry or liquid poolpolymerization process; U.S. Pat. No. 5,283,218 is directed towards theprepolymerization of a metallocene catalyst; U.S. Pat. Nos. 5,332,706and 5,473,028 have resorted to a particular technique for forming acatalyst by incipient impregnation; U.S. Pat. Nos. 5,427,991 and5,643,847 describe the chemical bonding of non-coordinating anionicactivators to supports; U.S. Pat. No. 5,492,975 discusses polymer boundmetallocene-type catalyst systems; U.S. Pat. No. 5,661,095 discussessupporting a metallocene-type catalyst on a copolymer of an olefin andan unsaturated silane; PCT publication WO 97/06186 published Feb. 20,1997 teaches removing inorganic and organic impurities after formationof the metallocene-type catalyst itself; PCT publication WO 97/15602published May 1, 1997 discusses readily supportable metal complexes; PCTpublication WO 97/27224 published Jul. 31, 1997 relates to forming asupported transition metal compound in the presence of an unsaturatedorganic compound having at least one terminal double bond; and EP-A2-811638 discusses using a metallocene catalyst and an activating cocatalystin a polymerization process in the presence of a nitrogen containingantistatic agent.

U.S. Pat. Nos. 4,942,147 and 5,362,823 discuss the addition ofautoacceleration inhibitors to prevent sheeting.

While all these possible solutions might reduce the level of fouling orsheeting somewhat, some are expensive to employ and/or may not reducefouling and sheeting to a level sufficient to successfully operate acontinuous process, particularly a commercial or large-scale process.

Thus, it would be advantageous to have a polymerization process capableof operating continuously with enhanced reactor operability and at thesame time produce new and improved polymers. It would also be highlybeneficial to have a continuously operating polymerization processhaving more stable catalyst productivities, reduced fouling/sheetingtendencies and increased duration of operation.

SUMMARY OF THE INVENTION

This invention provides a method of making a new and improved catalystcomposition, the catalyst composition itself and its use in apolymerizing process. Also, the invention is directed to the use of twoor more different compounds in the presence of a polymerization catalystthat react at a specified temperature during a polymerization process torelease at least one catalyst inhibitor. The most preferred compoundsare acid and base combinations, specifically Bronsted acids and Bronstedbases, or an oxidant and a reductant combination.

The method comprises the step of combining, contacting, blending and/ormixing any catalyst system, preferably a supported catalyst system, withat least two different compounds, preferably with at least one acidcompound and at least one base compound, such that at a specifiedtemperature the two different compounds, preferably the acid compoundand the base compound, react to form a catalyst inhibitor thatdeactivates the catalyst system. In the most preferred embodiment, theat least two different compounds, preferably the acid compound and basecompound, react at a temperature above the polymerization temperature,reactor temperature, to form a catalyst inhibitor, more preferably agaseous catalyst inhibitor. In one embodiment, the catalyst systemcomprises a conventional-type transition metal catalyst compound. In themost preferred embodiment the catalyst system comprises a bulky ligandmetallocene-type catalyst compound. The combination or use of an olefinpolymerization catalyst and the binary compounds, preferably the acidcompound and the base compound, is useful in any olefin polymerizationprocess. The preferred polymerization processes are a gas phase or aslurry phase process, most preferably a gas phase process.

In another preferred embodiment, the invention provides for a processfor polymerizing olefin(s) in the presence of a polymerization catalyst,and at least two different compounds, preferably an acid compound and abase compound, in a reactor at an operating temperature, wherein the twodifferent compounds, preferably the acid compound and base compound,react at a temperature above the operating temperature to form acatalyst inhibitor that reduces the effectiveness of the polymerizationcatalyst to polymerize olefin(s). In the most preferred embodiment, thecatalyst inhibitor renders the polymerization catalyst inactive.

In yet another preferred embodiment, the invention is directed to aprocess for polymerizing olefin(s) in the presence of a polymerizationcatalyst in a reactor under polymerization conditions, the processcomprising the steps (a) introducing at least one compound, preferablyan acid compound; and (b) introducing at least one different compound,preferably a base compound, wherein two compounds, preferably the acidand the base compounds react in the reactor to form at least onecatalyst inhibitor that reduces the effectiveness of the polymerizationcatalyst to polymerize olefin(s).

DETAILED DESCRIPTION OF THE INVENTION

Introduction

The invention is directed toward a method for making a catalystcomposition and to the catalyst composition itself. The invention alsorelates to a polymerization process having improved operability usingthe catalyst composition. While not being bound to any particulartheory, it is believed that one possible cause for reduced operability,especially sheeting and/or fouling, is the result of a catalyst'stendency to continue to polymerize well after its initial activation. Ithas been suprisingly discovered that using two or more compounds,preferably an acid compound and a base compound, or an oxidant and areductant, that react to form a catalyst inhibitor in combination with apolymerization catalyst results in the ability to control the catalyst'stendency for continuing to effectively polymerize olefin(s). It has alsobeen discovered that the reaction of the two or more compounds,preferably, the acid compound and the base compound, to form thecatalyst inhibitor is controllable. In the most preferred embodiment,the reaction is controlled by changing the acid compound. The presentinvention is useful in all types of polymerization processes, especiallya slurry or gas phase process.

Catalyst Components and Catalyst Systems

All polymerization catalysts including conventional-type transitionmetal catalysts and bulky ligand metallocene-type catalysts are suitablefor use in the polymerizing process of the invention. The following is anon-limiting discussion of the various polymerization catalysts usefulin the invention.

Conventional-Type Transition Metal Catalysts

Conventional-type transition metal catalysts are those traditionalZiegler-Natta catalysts and Phillips-type catalysts well known in theart. Examples of conventional-type transition metal catalysts arediscussed in U.S. Pat. Nos. 4,115,639, 4,077,904, 4,482,687, 4,564,605,4,721,763, 4,879,359 and 4,960,741 all of which are herein fullyincorporated by reference. The conventional-type transition metalcatalyst compounds that may be used in the present invention includetransition metal compounds from Groups 3 to 17, preferably 4 to 12, morepreferably 4 to 6 of the Periodic Table of Elements.

These conventional-type transition metal catalysts may be represented bythe formula: MR_(x), where M is a metal from Groups 3 to 17, preferablyGroup 4 to 6, more preferably Group 4, most preferably titanium; R is ahalogen or a hydrocarbyloxy group; and x is the valence of the metal M.Non-limiting examples of R include alkoxy, phenoxy, bromide, chlorideand fluoride. Non-limiting examples of conventional-type transitionmetal catalysts where M is titanium include TiCl₄, TiBr₄, Ti(OC₂H₅)₃Cl,Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)₃Cl, Ti(OC₃H₇)₂Cl₂, Ti(OC₂H₅)₂Br₂, TiCl₃. ⅓AlCl₃and Ti(OC₁₂H₂₅)Cl₃.

Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. The MgTiCl₆(ethyl acetate)₄ derivative is particularly preferred.

British Patent Application 2,105,355 and U.S. Pat. No. 5,317,036, hereinincorporated by reference, describes various conventional-type vanadiumcatalyst compounds. Non-limiting examples of conventional-type vanadiumcatalyst compounds include vanadyl trihalide, alkoxy halides andalkoxides such as VOCl₃, VOCl₂(OBu) where Bu=butyl and VO(OC₂H₅)₃;vanadium tetra-halide and vanadium alkoxy halides such as VCl₄ andVCl₃(OBu); vanadium and vanadyl acetyl acetonates and chloroacetylacetonates such as V(AcAc)₃ and VOCl₂(AcAc) where (AcAc) is an acetylacetonate. The preferred conventional-type vanadium catalyst compoundsare VOCl₃, VCl₄ and VOCl₂—OR where R is a hydrocarbon radical,preferably a C₁ to C₁₀ aliphatic or aromatic hydrocarbon radical such asethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl,tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetylacetonates.

Conventional-type chromium catalyst compounds, often referred to asPhillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, which areherein fully incorporated by reference.

Still other conventional-type transition metal catalyst compounds andcatalyst systems suitable for use in the present invention are disclosedin U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566, 4,376,062, 4,379,758,5,066,737, 5,763,723, 5,849,655, 5,852,144, 5,854,164 and 5,869,585 andpublished EP-A2 0 416 815 A2 and EP-A1 0 420 436, which are all hereinincorporated by reference.

Other catalysts may include cationic catalysts such as AlCl₃, and othercobalt, iron, nickel and palladium catalysts well known in the art. Seefor example U.S. Pat. Nos. 3,487,112, 4,472,559, 4,182,814 and 4,689,437all of which are incorporated herein by reference.

Typically, these conventional-type transition metal catalyst compoundsexcluding some conventional-type chromium catalyst compounds areactivated with one or more of the conventional-type cocatalystsdescribed below.

Conventional-Type Cocatalysts

Conventional-type cocatalyst compounds for the above conventional-typetransition metal catalyst compounds may be represented by the formulaM³M⁴ _(v)X² _(c)R³ _(b−c), wherein M³ is a metal from Group 1 to 3 and12 to 13 of the Periodic Table of Elements; M⁴ is a metal of Group 1 ofthe Periodic Table of Elements; v is a number from 0 to 1; each X² isany halogen; c is a number from 0 to 3; each R³ is a monovalenthydrocarbon radical or hydrogen; b is a number from 1 to 4; and whereinb minus c is at least 1. Other conventional-type organometalliccocatalyst compounds for the above conventional-type transition metalcatalysts have the formula M³R³ _(k), where M³ is a Group IA, IIA, IIBor IIIA metal, such as lithium, sodium, beryllium, barium, boron,aluminum, zinc, cadmium, and gallium; k equals 1, 2 or 3 depending uponthe valency of M³ which valency in turn normally depends upon theparticular Group to which M³ belongs; and each R³ may be any monovalentradical that include hydrocarbon radicals and hydrocarbon radicalscontaining a Group 13 to 16 element like fluoride, aluminum or oxygen ora combination thereof.

Non-limiting examples of conventional-type organometallic cocatalystcompounds useful with the conventional-type catalyst compounds describedabove include methyllithium, butyllithium, dihexylmercury,butylmagnesium, diethylcadmium, benzylpotassium, diethylzinc,tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium,di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminumalkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylaluminum,and tri-isobutylaluminum. Other conventional-type cocatalyst compoundsincludes mono-organohalides and hydrides of Group 2 metals, and mono- ordi-organohalides and hydrides of Group 3 and 13 metals. Non-limitingexamples of such conventional-type cocatalyst compounds includedi-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesiumchloride, ethylberyllium chloride, ethylcalcium bromide,di-isobutylaluminum hydride, methylcadmium hydride, diethylboronhydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesiumhydride, butylzinc hydride, dichloroboron hydride, di-bromo-aluminumhydride and bromocadmium hydride. Conventional-type organometalliccocatalyst compounds are known to those in the art and a more completediscussion of these compounds may be found in U.S. Pat. Nos. 3,221,002and 5,093,415, which are herein fully incorporated by reference.

Bulky Ligand Metallocene-Type Catalyst Compounds

Generally, bulky ligand metallocene-type catalyst compounds include halfand full sandwich compounds having one or more bulky ligands bonded toat least one metal atom. Typical bulky ligand metallocene-type compoundsare generally described as containing one or more bulky ligand(s) andone or more leaving group(s) bonded to at least one metal atom. In onepreferred embodiment, at least one bulky ligands is η-bonded to themetal atom, most preferably η⁵-bonded to the metal atom.

The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s), aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

In one embodiment, the bulky ligand metallocene-type catalyst compoundsof the invention are represented by the formula:L^(A)L^(B)MQ_(n)  (I)where M is a metal atom from the Periodic Table of the Elements and maybe a Group 3 to 12 metal or from the lanthanide or actinide series ofthe Periodic Table of Elements, preferably M is a Group 4, 5 or 6transition metal, more preferably M is a Group 4 transition metal, evenmore preferably M is zirconium, hafnium or titanium. The bulky ligands,L^(A) and L^(B), are open, acyclic or fused ring(s) or ring system(s)such as unsubstituted or substituted, cyclopentadienyl ligands orcyclopentadienyl-type ligands, heteroatom substituted and/or heteroatomcontaining cyclopentadienyl-type ligands. Non-limiting examples of bulkyligands include cyclopentadienyl ligands, cyclopentaphenanthreneylligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, azenylligands, azulene ligands, pentalene ligands, phosphoyl ligands, pyrrolylligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands andthe like, including hydrogenated versions thereof, for exampletetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B) may be anyother ligand structure capable of η-bonding to M, preferably η³-bondingto M and most preferably η⁵-bonding. In yet another embodiment, theatomic molecular weight (MW) of L^(A) or L^(B) exceeds 60 a.m.u.,preferably greater than 65 a.m.u. In another embodiment, L^(A) and L^(B)may comprise one or more heteroatoms, for example, nitrogen, silicon,boron, germanium, sulfur, oxygen and phosphorous, in combination withcarbon atoms to form an open, acyclic, or preferably a fused, ring orring system, for example, a hetero-cyclopentadienyl ancillary ligand.Other L^(A) and L^(B) bulky ligands include but are not limited to bulkyamides, phosphides, alkoxides, aryloxides, imides, carbolides,borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (I) only one of either L^(A) or L^(B) is present.

Independently, each L^(A) and L^(B) may be unsubstituted or substitutedwith a combination of substituent groups R. Non-limiting examples ofsubstituent groups R include one or more from the group selected fromhydrogen, or linear, branched alkyl radicals, or alkenyl radicals,alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals,aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonylradicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals,acyloxy radicals, acylamino radicals, aroylamino radicals, straight,branched or cyclic, alkylene radicals, or combination thereof. In apreferred embodiment, substituent groups R have up to 50 non-hydrogenatoms, preferably from 1 to 30 carbon, that can also be substituted withhalogens or heteroatoms or the like. Non-limiting examples of alkylsubstituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, includingall their isomers, for example tertiary butyl, isopropyl, and the like.Other hydrocarbyl radicals include fluoromethyl, fluroethyl,difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbylsubstituted organometalloid radicals including trimethylsilyl,trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

Other ligands may be bonded to the metal M, such as at least one leavinggroup Q. For the purposes of this patent specification and appendedclaims the term “leaving group” is any ligand that can be abstractedfrom a bulky ligand metallocene-type catalyst compound to form a bulkyligand metallocene-type catalyst cation capable of polymerizing one ormore olefin(s). In one embodiment, Q is a monoanionic labile ligandhaving a sigma-bond to M.

Non-limiting examples of Q ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike. Depending on the oxidation state of the metal, the value for n is0, 1 or 2 such that formula (I) above represents a neutral bulky ligandmetallocene-type catalyst compound.

In one embodiment, the bulky ligand metallocene-type catalyst compoundsof the invention include those of formula (I) where L^(A) and L^(B) arebridged to each other by a bridging group, A, such that the formula isrepresented byL^(A)AL^(B)MQ_(n)  (II)

These bridged compounds represented by formula (II) are known asbridged, bulky ligand metallocene-type catalyst compounds. L^(A), L^(B),M, Q and n are as defined above. Non-limiting examples of bridging groupA include bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, boron, germanium andtin atom or a combination thereof. Preferably bridging group A containsa carbon, silicon, iron or germanium atom, most preferably A contains atleast one silicon atom or at least one carbon atom. The bridging group Amay also contain substituent groups R as defined above includinghalogens. Non-limiting examples of bridging group A may be representedby R′₂C, R′₂Si, R′₂Si, R′₂Si, R′₂Ge, R′P, where R′ is independently, aradical group which is hydride, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, hydrocarbyl-substitutedorganometalloid, halocarbyl-substituted organometalloid, disubstitutedboron, disubstituted pnictogen, substituted chalcogen, or halogen or twoor more R′ may be joined to form a ring or ring system.

In one embodiment, the bulky ligand metallocene-type catalyst compoundsare those where the R substituents on the bulky ligands L^(A) and L^(B)of formulas (I) and (II) are substituted with the same or differentnumber of substituents on each of the bulky ligands. In anotherembodiment, the bulky ligands L^(A) and L^(B) of formulas (I) and (II)are different from each other.

Other bulky ligand metallocene-type catalyst compounds and catalystsystems useful in the invention may include those described in U.S. Pat.Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208,5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398,5,753,578, 5,854,363 and 5,856,547, 5,858,903, 5,859,158 and 5,929,266and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144,WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO 99/14221 andEuropean publications EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513 380,EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819, EP-B1-0 748 821 andEP-B1-0 757 996, all of which are herein fully incorporated byreference.

In one embodiment, bulky ligand metallocene-type catalysts compoundsuseful in the invention include bridged heteroatom, mono-bulky ligandmetallocene-type compounds. These types of catalysts and catalystsystems are described in, for example, PCT publication WO 92/00333, WO94/07928, WO 91/04257, WO 94/03506, WO96/00244 and WO 97/15602 and U.S.Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and5,264,405 and European publication EP-A-0 420 436, all of which areherein fully incorporated by reference.

In this embodiment, the bulky ligand metallocene-type catalyst compoundis represented by the formula:L^(C)AJMQ_(n)  (III)where M is a Group 3 to 16 metal atom or a metal selected from the Groupof actinides and lanthanides of the Periodic Table of Elements,preferably M is a Group 4 to 12 transition metal, and more preferably Mis a Group 4, 5 or 6 transition metal, and most preferably M is a Group4 transition metal in any oxidation state, especially titanium; L^(C) isa substituted or unsubstituted bulky ligand bonded to M; J is bonded toM; A is bonded to M and J; J is a heteroatom ancillary ligand; and A isa bridging group; Q is a univalent anionic ligand; and n is the integer0, 1 or 2. In formula (III) above, L^(C), A and J form a fused ringsystem. In an embodiment, L^(C) of formula (III) is as defined above forL^(A), A, M and Q of formula (III) are as defined above in formula (I).In formula (III) J is a heteroatom containing ligand in which J is anelement with a coordination number of three from Group 15 or an elementwith a coordination number of two from Group 16 of the Periodic Table ofElements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfuratom with nitrogen being most preferred.

In another embodiment, the bulky ligand type metallocene-type catalystcompound is a complex of a metal, preferably a transition metal, a bulkyligand, preferably a substituted or unsubstituted pi-bonded ligand, andone or more heteroallyl moieties, such as those described in U.S. Pat.Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which areherein fully incorporated by reference.

In an embodiment, the bulky ligand metallocene-type catalyst compound isrepresented by the formula:L^(D)MQ₂(YZ)X_(n)  (IV)where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transitionmetal, and most preferably a Group 4, 5 or 6 transition metal; LD is abulky ligand that is bonded to M; each Q is independently bonded to Mand Q₂(YZ) forms a unicharged polydentate ligand; A or Q is a univalentanionic ligand also bonded to M; X is a univalent anionic group when nis 2 or X is a divalent anionic group when n is 1; n is 1 or 2.

In formula (IV), L and M are as defined above for formula (I). Q is asdefined above for formula (I), preferably Q is selected from the groupconsisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

In another embodiment of the invention, the bulky ligandmetallocene-type catalyst compounds are heterocyclic ligand complexeswhere the bulky ligands, the ring(s) or ring system(s), include one ormore heteroatoms or a combination thereof. Non-limiting examples ofheteroatoms include a Group 13 to 16 element, preferably nitrogen,boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examplesof these bulky ligand metallocene-type catalyst compounds are describedin WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874005 and U.S. Pat. Nos. 5,637,660, 5,539,124, 5,554,775, 5,756,611,5,233,049, 5,744,417, and 5,856,258 all of which are herein incorporatedby reference.

In another embodiment, the bulky ligand metallocene-type catalystcompounds are those complexes known as transition metal catalysts basedon bidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference.

In another embodiment, the bulky ligand metallocene-type catalystcompounds are those described in PCT publications WO 99/01481 and WO98/42664, which are fully incorporated herein by reference.

In one embodiment, the bulky ligand metallocene-type catalyst compoundis represented by the formula:((Z)XA_(t)(YJ))_(q)MQ_(n)  (V)where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X,Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.Other Bulky Ligand Metallocene-Type Catalyst Compounds

It is within the scope of this invention, in one embodiment, that thebulky ligand metallocene-type catalyst compounds include complexes ofNi²⁺ and Pd²⁺ described in the articles Johnson, et al., “New Pd(II)-and Ni(II)-Based Catalysts for Polymerization of Ethylene anda-Olefins”, J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson, et al.,“Copolymerization of Ethylene and Propylene with Functionalized VinylMonomers by Palladium(II) Catalysts”, J. Am. Chem. Soc., 1996, 118,267-268, and WO 96/23010 published Aug. 1, 1996, WO 99/02472, U.S. Pat.Nos. 5,852,145, 5,866,663 and 5,880,241, which are all herein fullyincorporated by reference. These complexes can be either dialkyl etheradducts, or alkylated reaction products of the described dihalidecomplexes that can be activated to a cationic state by the activators ofthis invention described below.

Also included as bulky ligand metallocene-type catalyst are thosediimine based ligands of Group 8 to 10 metal compounds disclosed in PCTpublications WO 96/23010 and WO 97/48735 and Gibson, et. al., Chem.Comm., pp. 849-850 (1998), all of which are herein incorporated byreference.

Other bulky ligand metallocene-type catalysts are those Group 5 and 6metal imido complexes described in EP-A2-0 816 384 and U.S. Pat. No.5,851,945, which is incorporated herein by reference. In addition, bulkyligand metallocene-type catalysts include bridged bis(arylamido) Group 4compounds described by D. H. McConville, et al., in Organometallics1195, 14, 5478-5480, which is herein incorporated by reference. Otherbulky ligand metallocene-type catalysts are described as bis(hydroxyaromatic nitrogen ligands) in U.S. Pat. No. 5,852,146, which isincorporated herein by reference. Other metallocene-type catalystscontaining one or more Group 15 atoms include those described in WO98/46651, which is herein incorporated herein by reference.

It is also contemplated that in one embodiment, the bulky ligandmetallocene-type catalysts of the invention described above includetheir structural or optical or enantiomeric isomers (meso and racemicisomers, for example see U.S. Pat. No. 5,852,143, incorporated herein byreference) and mixtures thereof.

Activator and Activation Methods for the Bulky Ligand Metallocene-TypeCatalyst Compounds

The above described bulky ligand metallocene-type catalyst compounds aretypically activated in various ways to yield catalyst compounds having avacant coordination site that will coordinate, insert, and polymerizeolefin(s), an activated polymerization catalyst.

For the purposes of this patent specification and appended claims, theterm “activator” is defined to be any compound or component or methodwhich can activate any of the bulky ligand metallocene-type catalystcompounds of the invention as described above. Non-limiting activators,for example may include a Bronsted acid or a non-coordinating ionicactivator or ionizing activator or any other compound including Bronstedbases, aluminum alkyls, conventional-type cocatalysts and combinationsthereof that can convert a neutral bulky ligand metallocene-typecatalyst compound to a catalytically active bulky ligand metallocenecation. It is within the scope of this invention to use alumoxane ormodified alumoxane as an activator, and/or to also use ionizingactivators, neutral or ionic, such as tri (n-butyl) ammonium tetrakis(pentafluorophenyl) boron, a trisperfluorophenyl boron metalloidprecursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983) or combinationthereof, that would ionize the neutral bulky ligand metallocene-typecatalyst compound.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing both a bulkyligand metallocene-type catalyst cation and a non-coordinating anion arealso contemplated, and are described in EP-A-0 426 637, EP-A-0 573 403and U.S. Pat. No. 5,387,568, which are all herein incorporated byreference.

There are a variety of methods for preparing alumoxane and modifiedalumoxanes, non-limiting examples of which are described in U.S. Pat.Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801,5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838,5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166 and 5,856,256 andEuropean publications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218and EP-B1-0 586 665, and PCT publication WO 94/10180, all of which areherein fully incorporated by reference.

Organoaluminum compounds useful as activators include triethylaluminum,triisobutylaluminum, trimethylaluminum, tri-n-hexyl aluminum and thelike.

Ionizing compounds may contain an active proton, or some other cationassociated with but not coordinated to or only loosely coordinated tothe remaining ion of the ionizing compound. Such compounds and the likeare described in European publications EP-A-0 570 982, EP-A-0 520 732,EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, andU.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025,5,384,299 and 5,502,124 and U.S. patent application Ser. No. 08/285,380,filed Aug. 3, 1994, all of which are herein fully incorporated byreference.

Other activators include those described in PCT publication WO 98/07515such as tris (2,2′,2″-nonafluorobiphenyl) fluoroaluminate, whichpublication is fully incorporated herein by reference. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference. Other activators include aluminum/boroncomplexes as described in EP 608 830 B1, which is herein incorporated byreference. WO 98/09996 incorporated herein by reference describesactivating bulky ligand metallocene-type catalyst compounds withperchlorates, periodates and iodates including their hydrates. WO98/30602 and WO 98/30603 incorporated by reference describe the use oflithium (2,2′-bisphenyl-ditrimethylsilicate).4THF as an activator for abulky ligand metallocene-type catalyst compound. EP-B1-0 781 299describes using a silylium salt in combination with a non-coordinatingcompatible anion. Also, methods of activation such as using radiation(see EP-B1-0 615 981 herein incorporated by reference), electro-chemicaloxidation, and the like are also contemplated as activating methods forthe purposes of rendering the neutral bulky ligand metallocene-typecatalyst compound or precursor to a bulky ligand metallocene-type cationcapable of polymerizing olefins. Other activators or methods foractivating a bulky ligand metallocene-type catalyst compound aredescribed in for example, U.S. Pat. Nos. 5,849,852, 5,859,653 and5,869,723 and PCT WO 98/32775, which are herein incorporated byreference.

It is also within the scope of this invention that the above describedbulky ligand metallocene-type catalyst compounds can be combined withone or more of the catalyst compounds represented by formulas (I)through (V) with one or more activators or activation methods describedabove.

It is further contemplated by the invention that other catalysts can becombined with the bulky ligand metallocene-type catalyst compounds ofthe invention. For example, see U.S. Pat. Nos. 4,937,299, 4,935,474,5,281,679, 5,359,015, 5,470,811, and 5,719,241 all of which are hereinfully incorporated herein reference. It is also contemplated that anyone of the bulky ligand metallocene-type catalyst compounds of theinvention have at least one fluoride or fluorine containing leavinggroup as described in U.S. application Ser. No. 09/191,916 filed Nov.13, 1998.

In another embodiment of the invention one or more bulky ligandmetallocene-type catalyst compounds or catalyst systems may be used incombination with one or more conventional-type catalyst compounds orcatalyst systems. Non-limiting examples of mixed catalysts and catalystsystems are described in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432,5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264,5,723,399 and 5,767,031 and PCT Publication WO 96/23010 published Aug.1, 1996, all of which are herein fully incorporated by reference.

Supports, Carriers and General Supporting Techniques

The above described conventional-type transition metal catalystcompounds and catalyst systems and bulky ligand metallocene-typecatalyst compounds and catalyst systems may be combined with one or moresupport materials or carriers using one of the support methods wellknown in the art or as described below. For example, in a most preferredembodiment, a bulky ligand metallocene-type catalyst compound orcatalyst system is in a supported form, for example deposited on,contacted with, vapourized with, bonded to, or incorporated within,adsorbed or absorbed in, or on, a support or carrier.

The terms “support” or “carrier” are used interchangeably and are anysupport material, preferably a porous support material, more preferablyan inorganic support or an organic support. Inorganic supports arepreferred for example inorganic oxides and inorganic chlorides. Othercarriers include resinous support materials such as polystyrene,functionalized or crosslinked organic supports, such as polystyrenedivinyl benzene polyolefins or polymeric compounds, zeolites, clays,talc, or any other organic or inorganic support material and the like,or mixtures thereof. The most preferred carriers are inorganic oxidesthat include those Group 2, 3, 4, 5, 13 or 14 metal oxides. Thepreferred supports include silica, alumina, silica-alumina, magnesiumchloride, and mixtures thereof.

Other useful supports include magnesia, titania, zirconia,montmorillonite (EP-B1 0 511 665) and the like. Also, combinations ofthese support materials may be used, for example, silica-chromium,silica-alumina, silica-titania and the like.

It is preferred that the carrier, most preferably an inorganic oxide,has a surface area in the range of from about 10 to about 700 m²/g, porevolume in the range of from about 0.1 to about 4.0 cc/g and averageparticle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the carrier is in the range of fromabout 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5cc/g and average particle size of from about 10 to about 200 μm. Mostpreferably the surface area of the carrier is in the range is from about100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g andaverage particle size is from about 5 to about 100 μm. The average poresize of the carrier of the invention typically has pore size in therange of from 10 to 1000 Å, preferably 50 to about 500Å, and mostpreferably 75 to about 350 Å.

Examples of supporting the bulky ligand metallocene-type catalystsystems of the invention are described in U.S. Pat. Nos. 4,701,432,4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892,5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766,5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835, 5,625,015,5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402,5,731,261, 5,759,940, 5,767,032, 5,770,664 and 5,846,895 and U.S.application Ser. No. 271,598 filed Jul. 7, 1994 and Ser. No. 788,736filed Jan. 23, 1997 and PCT publications WO 95/32995, WO 95/14044, WO96/06187 and WO 97/02297, and EP-B1-0 685 494 all of which are hereinfully incorporated by reference. Examples of supportingconventional-type transition metal catalyst compounds are also wellknown in the art.

There are various other methods in the art for supporting apolymerization catalyst compound or catalyst system of the invention.For example, the bulky ligand metallocene-type catalyst compound of theinvention may contain a polymer bound ligand as described in U.S. Pat.Nos. 5,473,202 and 5,770,755, which is herein fully incorporated byreference; the bulky ligand metallocene-type catalyst system of theinvention may be spray dried as described in U.S. Pat. No. 5,648,310,which is herein fully incorporated by reference; the support used withthe bulky ligand metallocene-type catalyst system of the invention isfunctionalized as described in European publication EP-A-0 802 203,which is herein fully incorporated by reference, or at least onesubstituent or leaving group is selected as described in U.S. Pat. No.5,688,880, which is herein fully incorporated by reference.

In a preferred embodiment, the invention provides for a supported bulkyligand metallocene-type catalyst system that includes an antistaticagent or surface modifier that is used in the preparation of thesupported catalyst system as described in PCT publication WO 96/11960,which is herein fully incorporated by reference. The catalyst systems ofthe invention can be prepared in the presence of an olefin, for examplehexene-1.

In another embodiment, the bulky ligand metallocene-type catalyst systemcan be combined with a carboxylic acid salt of a metal ester, forexample aluminum carboxylates such as aluminum mono, di- andtri-stearates, aluminum octoates, oleates and cyclohexylbutyrates, asdescribed in U.S. application Ser. No. 09/113,216, filed Jul. 10, 1998.

A preferred method for producing the supported bulky ligandmetallocene-type catalyst system of the invention is described below andis described in U.S. application Ser. No. 265,533, filed Jun. 24, 1994and Ser. No. 265,532, filed Jun. 24, 1994 and PCT publications WO96/00245 and WO 96/00243 both published Jan. 4, 1996, all of which areherein fully incorporated by reference. In this preferred method, thebulky ligand metallocene-type catalyst compound is slurried in a liquidto form a metallocene solution and a separate solution is formedcontaining an activator and a liquid. The liquid may be any compatiblesolvent or other liquid capable of forming a solution or the like withthe bulky ligand metallocene-type catalyst compounds and/or activator ofthe invention. In the most preferred embodiment the liquid is a cyclicaliphatic or aromatic hydrocarbon, most preferably toluene. The bulkyligand metallocene-type catalyst compound and activator solutions aremixed together and added to a porous support or the porous support isadded to the solutions such that the total volume of the bulky ligandmetallocene-type catalyst compound solution and the activator solutionor the bulky ligand metallocene-type catalyst compound and activatorsolution is less than four times the pore volume of the porous support,more preferably less than three times, even more preferably less thantwo times; preferred ranges being from 1.1 times to 3.5 times range andmost preferably in the 1.2 to 3 times range.

Procedures for measuring the total pore volume of a porous support arewell known in the art. Details of one of these procedures is discussedin Volume 1, Experimental Methods in Catalytic Research (Academic Press,1968) (specifically see pages 67-96). This preferred procedure involvesthe use of a classical BET apparatus for nitrogen absorption. Anothermethod well known in the art is described in Innes, Total Porosity andParticle Density of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3,Analytical Chemistry 332-334 (March, 1956).

The mole ratio of the metal of the activator component to the metal ofthe supported bulky ligand metallocene-type catalyst compounds are inthe range of between 0.3:1 to 1000:1, preferably 20:1 to 800:1, and mostpreferably 50:1 to 500:1. Where the activator is an ionizing activatorsuch as those based on the anion tetrakis(pentafluorophenyl)boron, themole ratio of the metal of the activator component to the metalcomponent of the bulky ligand metallocene-type catalyst is preferably inthe range of between 0.3:1 to 3:1.

In one embodiment of the invention, olefin(s), preferably C₂ to C₃₀olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of theconventional-type transition metal catalyst system and/or a bulky ligandmetallocene-type catalyst system of the invention prior to the mainpolymerization. The prepolymerization can be carried out batchwise orcontinuously in gas, solution or slurry phase including at elevatedpressures. The prepolymerization can take place with any olefin monomeror combination and/or in the presence of any molecular weightcontrolling agent such as hydrogen. For examples of prepolymerizationprocedures, see U.S. Pat. Nos. 4,748,221, 4,789,359, 4,923,833,4,921,825, 5,283,278 and 5,705,578 and European publication EP-B-0279863 and PCT Publication WO 97/44371 all of which are herein fullyincorporated by reference. In this embodiment, the prepolymerization iseither in the presence of the at least two compounds, preferably theacid and base compounds, or the at least two compounds are added afterthe prepolymerization, but prior to the main polymerization, or simplyadded to the reactor with a already formed prepolymerized catalyst or acombination thereof. For the purposes of this patent specification andappended claims only, prepolymerization is considered a method forimmobilizing a catalyst system and therefore considered to form asupported catalyst system.

Compound Combinations

There are various compounds that can be used to form a catalystinhibitor to control the kinetics of an olefin polymerization catalyst.In the preferred embodiment, the invention relates to the use of two ormore different compounds in the presence of a polymerization catalystthat react at a specified temperature during a polymerization process torelease at least one catalyst inhibitor. In one embodiment, at least oneof the compounds having a weight loss of no greater than 20 weightpercent, preferably less than 10 weight percent, more preferably lessthan 5 weight percent, even more preferably less than 2 weight percentand most preferably less than 1 weight percent measured using a standardthermogravimetric analysis (TGA) at 80° C. for 20 minutes. In anotherembodiment of the invention at least one of the compounds has adielectric constant greater than 2, preferably greater than 5, morepreferably greater than 10 and/or a melting temperature in the range offrom 0° C. to 200° C., preferably from 10° C. to 180° C., morepreferably from 40° C. to 150° C., and most preferably from 80° C. to130° C. Other compounds include at least one oxidant or at least onereductant. The most preferred compounds are acid and base combinations,specifically Bronsted acids and Bronsted bases. Combinations ofacid/base and oxidant/reductant are also contemplated for use in thepresent invention. In addition to the preferred acid/base combinations,non-limiting examples of others include one or more of: 1)dithiodibutyric acid and KNO₃; 2) condensation of a carbonyl compoundwith an amine to give an imine and water; 3) reaction of an aldehyde anda rhodium-based catalyst to liberate carbon monoxide; 4) condensation ofan aldehyde and a ketone, or two aldehydes, to give an unsaturatedcarbonyl product and water; 5) oxidative decarboxylation of acids withlead tetraacetate to give olefins and carbon dioxide; and 6) oxidativecleavage of 1,2-diols with periodic acid to yield two aldehydes. All ofthese combination of compounds can be used with polymerization catalystsin a polymerization process of the invention so as to release a catalystinhibitor.

Acid and Base Compounds

It is preferred that the acid and base compounds, preferably Bronstedacid and Bronsted base compounds, when combined or contacted with eachother are essentially or completely unreactive with one another undercertain conditions. These conditions depend on for example, theparticular polymerization process in which they are to be used and/orthe delivery mechanism for their introduction to a reactor. However,when combined or contacted with each at another set of conditions, forexample under polymerization conditions, they react to form a catalystinhibitor that will essentially or completely render a catalyst systemcatalytically inactive.

The acid compounds may be represented by the following general formula:X—H,where X—H is an acid, preferably a Bronsted acid (Bronsted, J. N. Rec.Trav. Chim. 1923, 42, 718), with a pKa of less than 20, preferably lessthan 15, more preferably less than 10, most preferred less than 5. Someclasses of Bronsted acids include ketones, alcohols, ammonium salts,nitriles, nitro compounds, acetylenes, phenols, carboxylic acids andmineral acids. Examples of these classes include acetophenone,adamantanol, anilinium chloride, diphenyl-acetonitrile, picrolonic acid,phenylacetylene, phenol, benzoic acid and tungstic acid. Most preferredare carboxylic acids, including o-toluic acid, tropic acid,4-octyloxybenzoic acid, 4-bromophenylacetic acid, 2-phenoxybenzoic acid,3,4,5-triethoxybenzoic acid and 2,4-dimethoxybenzoic acid.

Especially preferred are acids having a high density of functionalgroups, such as malic acid and glutaric acid.

Non-limiting examples of acid compounds include 3-methyladipic acid,DL-malic acid, tropic acid, glutaric acid, ketoglutaric acid, pimelicacid, mandelic acid, 3-t-butyladipic acid and L-malic acid.

The base compounds may be represented by the following general formula:X—B,where X—B is a base, preferably Bronsted base, where the conjugate acidhas a pKa of greater than −5 and most preferably greater than 0. Someclasses of Bronsted bases include enolate anions, alkoxides, hydroxides,amides, deprotonated nitrites and nitro compounds, acetylides,phenoxides, carboxylates and various mineral salts. Examples of theseclasses include lithium acetophenone enolate, lithium adamantanoxide,sodium amide, sodium diphenylacetonitrile, sodium picrolonate,lithiumphenylacetylene, potassium phenoxide, magnesium benzoate, andcesium tungstate. More preferred are compounds, which upon conversion tothe base form become volatile, and thus, are more capable of renderingthe catalyst inactive. Examples of these include lithium carbonate,calcium carbonate, potassium bicarbonate, sodium hydroxide, lithiummethoxide, magnesium phenoxide, potassium acetate and lithium acetonate.Most preferred are carbonate and hydroxide salts.

Non-limiting examples of base compounds include potassium carbonate,calcium carbonate, sodium carbonate, barium carbonate, zinc carbonatehydroxide hydrate, magnesium carbonate hydroxide hydrate, calciumhydroxide, sodium hydroxide, magnesium hydroxide and aluminum hydroxide.

In the most preferred embodiment, the acid compound or the base compoundare solids, preferably both the acid and the base compound are solids.

The conditions at which the catalyst inhibitor is produced may becontrolled by varying the acid and base compounds, most preferably theacid compound. A preferred way for tuning the reaction of the acid andbase compounds is by changing the temperature at which the catalystinhibitor is formed. This may be done by choosing the meltingtemperature of the acid compound or the base compound. In oneembodiment, the acid compound and/or the base compound has a meltingpoint in the range of from 50° C. to about 130° C., preferably in therange of from about 60° C. to about 120° C., more preferably in therange of from 70° C. to about 110° C., and most preferably in the rangeof from 80° C. to about 105° C.

In another embodiment, the acid compound or the base compound has amelting point greater than 60° C., preferably greater than 70° C., morepreferably greater than 75° C., and most preferably greater than 80° C.

In one preferred embodiment, the acid/base combination is tropic acidwith lithium carbonate. Other acid/base combinations, one or more acidswith one or more bases, include the acids: glutaric acid, methyl adipicacid, L-malic acid, 4-octyloxybenzoic acid, 3-t-butyladipic acid,ketoglutaric acid, tropic acid and DL-malic acid; with the followingbases: lithium carbonate, sodium carbonate, potassium carbonate, calciumcarbonate, calcium hydroxide, magnesium hydroxide and magnesiumcarbonate hydroxide.

The preferred combinations of the acid and base compounds are those thatreact quickly and release a catalyst inhibitor in high yield. Moreover,it was found that the light-off temperature for the catalyst inhibitorrelease does not entirely depend on the melting point(s) of theacid/base components but can be tuned by proper selection of theacid-base pair. The melting point of the acid and/or base may becontrolled in an embodiment using dopants or mixtures of acid and/orbase compounds.

Insolubility in hydrocarbons is indispensable for slurry and solutionphase reactions. If desired, a third component (adjuvant) can be addedthat facilitates the reaction of the acid with the base (e.g., a fluxingagent). This adjuvant might also precipitate the reaction between theacid and base by virtue of melting at the selected temperature. Examplesof preferred combinations include L-malic acid with calcium carbonate,DL-malic acid with potassium carbonate, tropic acid with lithiumcarbonate, octyloxybenzoic acid with sodium carbonate and L-malic acidwith magnesium hydroxide. Examples of adjuvants might include aluminumdistearate, sodium dodecylbenenesulfonate, polyethylene glycol andpotassium laurate.

In an embodiment, one of either the acid or the base may have a lowermelting point than the other, however, it is preferred that acid andbase compounds are solids in the temperature range of from 25° C. tonormal reaction conditions of temperature in the reactor duringpolymerization. Normal polymerization temperatures vary depending on theprocess used and/or the polymer produced. Typically polymerizationtemperatures in a gas phase process are in the range of 50° C. to about120° C., more preferably from about 60° C. to about 110° C., mostpreferably from about 65° C. to about 100° C. Other polymerizationtemperatures are discussed later in this patent specification. Inaddition, in one embodiment, the two different compounds, preferably theacid and base compounds react at a temperature that is greater than 5°C. above the polymerization temperature.

The most preferred acid compounds generally include di- and tri-acidshaving a very low vapour pressure, a low hydrocarbon solubility,preferably no vapor pressure. Also preferred are acid compounds thathave a low toxicity.

Other preferred properties for the acid and base compounds include thefollowing considerations: 1) tunable so that its onset temperature(acid/base reaction) can be customized for a given process; 2) lowtoxicity; 3) not volatile as a solid; 4) responds quickly over a narrowtemperature range; 5) gives a high yield of catalyst inhibitor(s) on aweight basis; 6) unaffected by the type of catalyst; 7) operates undervarious reactor conditions; 8) evenly distributed throughout thereactor, and preferably does not enter the recycle line; 9) notsignificantly affect the pelletizing process; 10) not adversely affectdownstream polymer properties; and 11) easily handled.

In a preferred embodiment, the acid and base compounds are polarcompounds where the acid compound has at least one —OH functionality andthe base compound has at least one —O functionality, preferably a —COfunctionality. Most preferably these polar compounds are insoluble inaliphatic hydrocarbons.

The most preferred combination is L-malic acid and a carbonate compound,preferably calcium carbonate. The reaction of malic acid and calciumcarbonate results in the generation of at least two non-limitingexamples of catalyst inhibitors, water and carbon dioxide. Otherby-products that may be formed include calcium maleate. Other possiblenon-limiting catalyst inhibitors include alcohols, ketones, acetylenes,dienes, ammonia, amines, carboxylic acids, nitrites, nitro compounds.

In an embodiment, the acid and base compounds are used in a mole ratioof from 50:1 to 1:15, preferably from about 2:1 to 1:2.

Methods for Using the Combination of Compounds

The use of the at least two different compounds, preferably the acid andbase compounds, of the invention can vary. For example, the acid andbase compounds can be added or introduced with or without a catalystdirectly to a polymerization process. The acid and base compounds may becombined prior to introducing them to a polymerization process, or theacid and base compounds may be added separately and/or simultaneously tothe reactor. In an embodiment, the acid and base compounds are contactedwith a catalyst compound prior to being introduced to the reactor. In analternative embodiment, the acid compound is contacted with the catalystcompound and the base compound is added separately. Other embodimentsmay include placing the acid compound and/or the base compound and/oroxidant and/or reductant on a support material and then introducing thesupport material to the polymerization reactor.

The at least two compounds, preferably the acid and base compounds, maybe introduced in one embodiment in the recycle stream of a gas phasepolymerization process or below the distributor plate or in a regionwithin the reactor where the tendency for sheeting to occur is high. Thedetails of a gas phase polymerization process is discussed later in thispatent specification.

In yet another embodiment, the at least two compounds, preferably theacid and base compounds, are used in combination with an unsupportedcatalyst system.

In the most preferred embodiment, the acid and base compounds are usedwith a supported catalyst system. A most preferred method for making asupported catalyst system of the invention generally involves thecombining, contacting, blending, bonding and/or mixing any of the abovedescribed catalyst compounds, preferably a bulky ligand metallocene-typecatalyst compound using any of the techniques previously described.

In one embodiment of the method of the invention, a catalyst compound iscombined, contacted, bonded, blended, and/or mixed with at least oneacid compound and at least one base compound or with at least onereductant and at least one oxidant. In a most preferred embodiment, thecatalyst compound is a conventional-type transition metal catalystand/or a bulky ligand metallocene-type catalyst supported on a carrier.In one embodiment, the acid and base compounds are in a mineral oilslurry with or without a catalyst system, preferably with a supportedcatalyst system that is introduced to a polymerization process. It ispossible to improve the flow to a reactor of a polymerization catalysthaving been combined with the acid/base combination using Kaydol 350mineral oil or a flow aid such as TS 610 Cabosil, available from CabotCorporation, Tuscola, Ill.

In one embodiment, the flow and the performance of the acid/baseinteraction is improved by modifying the particle size of the acidcompound and/or the base compound. In a preferred embodiment, theparticle size of the acid and/or base compound is less than 100μ,preferably less than 50μ.

In another embodiment, the steps of the method of the invention includeforming a polymerization catalyst, preferably forming a supportedpolymerization catalyst, and contacting the polymerization catalyst,preferably the supported polymerization catalyst, with at least one acidcompound and at least one base compound and/or at least one reductantand at least one oxidant. In a preferred method, the polymerizationcatalyst comprises a catalyst compound, an activator and a carrier,preferably the polymerization catalyst is a supported bulky ligandmetallocene-type catalyst.

In one embodiment of the method of the invention at least two differentcompounds, preferably the acid and base compounds, are contacted withthe catalyst system, preferably a supported catalyst system, mostpreferably a supported bulky ligand metallocene-type catalyst systemunder ambient temperatures and pressures. Preferably the contacttemperature for combining the polymerization catalyst and the acid andbase compounds is in the range of from 0° C. to about 100° C., morepreferably from 15° C. to about 75° C., most preferably at about ambienttemperature and pressure.

In a preferred embodiment, the contacting of the polymerization catalystand the at least two compounds, preferably the acid and base compounds,is performed under an inert gaseous atmosphere, such as nitrogen.However, it is contemplated that the combination of the polymerizationcatalyst and the acid and base compounds may be performed in thepresence of olefin(s), solvents, hydrogen and the like.

In one embodiment, the acid and/or base compounds and/or oxidant andreductant may be added at any stage during the preparation. It isunderstood by those in the art that in choosing acid/base compound pairsfor example, that the compounds do not react with each other in asubstantial way, preferably not during preparation.

In one embodiment of the method of the invention, the polymerizationcatalyst and the acid and base compounds are combined in the presence ofa liquid, for example the liquid may be a mineral oil, toluene, hexane,isobutane or a mixture thereof. In a more preferred method the acid andbase compounds are combined with a polymerization catalyst that has beenformed in a liquid, preferably in a slurry, or combined with asubstantially dry or dried, polymerization catalyst that has been placedin a liquid and reslurried.

Preferably, prior to use, the polymerization catalyst is contacted withthe acid and base compounds for a period of time greater than a second,preferably from about 1 minute to about 48 hours, more preferably fromabout 10 minutes to about 10 hours, and most preferably from about 30minutes to about 6 hours. The period of contacting refers to the mixingtime only.

In an embodiment, the mole ratio of the base and acid compounds to themetal of the polymerization catalyst is the range from 5000 to about0.2, preferably from about 1000 to about 0.5, more preferably from about500 to about 1, and most preferably from about 250 to about 10.

In another embodiment, the weight ratio of the base and the acidcompounds to the weight of the polymerization catalyst (includingsupport if a supported polymerization catalyst) is the range from 100 to0.001, preferably from about 10 to about 0.01, more preferably from 5 to0.1, and most preferably from 2 to about 0.2.

Mixing techniques and equipment contemplated for use in the method ofthe invention are well known. Mixing techniques may involve anymechanical mixing means, for example shaking, stirring, tumbling, androlling. Another technique contemplated involves the use offluidization, for example in a fluid bed reactor vessel where circulatedgases provide the mixing. Non-limiting examples of mixing equipment forcombining, a solid polymerization catalyst and the acid and basecompounds include a ribbon blender, a static mixer, a double coneblender, a drum tumbler, a drum roller, a dehydrator, a fluidized bed, ahelical mixer and a conical screw mixer.

In a preferred embodiment of the invention the catalyst system of theinvention is supported on a carrier, preferably the supported catalystsystem is substantially dried, preformed, substantially dry and/or freeflowing. In an especially preferred method of the invention, thepreformed supported catalyst system is contacted with at least one acidcompound and at least one base compound. The acid and base compounds maybe in solution or slurry or in a dry state, preferably the acid and basecompounds are in a substantially dry or dried state.

In an embodiment, the method of the invention provides for co-injectingan unsupported polymerization catalyst and the acid and base compoundsor oxidant and reductant into the reactor. In one embodiment thepolymerization catalyst is used in the unsupported form, preferably in aliquid form such as described in U.S. Pat. Nos. 5,317,036 and 5,693,727and European publication EP-A-0 593 083, all of which are hereinincorporated by reference. The polymerization catalyst in liquid formcan be fed with the acid and base compounds together or separately to areactor using the injection methods described in PCT publication WO97/46599, which is fully incorporated herein by reference. Where anunsupported bulky ligand metallocene-type catalyst system is used themole ratio of the metal of the activator component to the metal of thebulky ligand metallocene-type catalyst compound is in the range ofbetween 0.3:1 to 10,000:1, preferably 100:1 to 5000:1, and mostpreferably 500:1 to 2000:1.

In one embodiment, the polymerization catalyst has a productivitygreater than 1500 grams of polymer per gram of catalyst, preferablygreater than 2000 grams of polymer per gram of catalyst, more preferablygreater than 2500 grams of polymer per gram of catalyst and mostpreferably greater than 3000 grams of polymer per gram of catalyst. Inone embodiment, when the at least two different compounds, preferablythe acid and base compounds of the invention, react to form a catalystinhibitor, the polymerization catalyst productivity is reduced to lessthan 1500 grams of polymer per gram of catalyst, preferably less than1000 grams of polymer per gram of catalyst, more preferably less than500 grams of polymer per gram of catalyst, even more preferably lessthan 100 grams of polymer per gram of catalyst, and still even morepreferably less than 25 grams of polymer per gram of catalyst and mostpreferably to less than is measurably possible or 0 grams of polymer pergram of catalyst.

The at least two different compounds, preferably the acid and base, maybe used together or the acid used separately from the base, with orseparate from the catalyst. In one embodiment, a binder is used to holdthe at least two different compounds, the acid to the base, the acid orthe base to the catalyst, or the acid and the base and the catalyst, orsimply to facilitate the reaction between the acid and the base. Whilenot wishing to be bound to any theory, binders may help facilitate thereaction of the acid and base. Also, a support material and/or a flowaid can be included. The binder may be added to the catalyst in anynumber of ways, for instance the binder can be added just after thecatalyst is made and is still in a slurry state or prior to evaporationof any liquid in which the catalyst was prepared. Non-limiting examplesof binders include polyethylene oxide, polyethylene/propylene oxide,mineral oil, silica, alumina, silicone oil, various waxes such ascarnauba wax, surfactants such as sodium dodecylbenzene sulfonate andchelating agents such as EDTA.

The at least two different compounds, preferably the acid and basecomponents may be combined with agents that would facilitate thereaction between the acid and base components at the trigger temperatureand/or help dissipate static charge build up and/or modify the flowproperties of the material and/or improve free flow of powders byreducing powder bed packing, decreasing particle coherence, and reducinginterparticle friction. Non-limiting examples of these agents includesilica such as cabosil, clays, surfactants such as esters of fattyacids, metal salts of fatty acids, silica, metal halides, solvated metalhalides, amines, polyoxyethylene and polyoxypropylene and theirderivatives, and sulfonates.

Polymerization Process

The catalyst system including the at least two different compounds, theacid and base compounds, and the oxidants and reductants of theinvention described above are suitable for use in any prepolymerizationand/or polymerization process over a wide range of temperatures andpressures. The temperatures may be in the range of from −60° C. to about280° C., preferably from 50° C. to about 200° C., and the pressuresemployed may be in the range from 1 atmosphere to about 500 atmospheresor higher.

Polymerization processes include solution, gas phase, slurry phase and ahigh pressure process or a combination thereof. Particularly preferredis a gas phase or slurry phase polymerization of one or more olefins atleast one of which is ethylene or propylene.

In one embodiment, the process of this invention is directed toward asolution, high pressure, slurry or gas phase polymerization process ofone or more olefin monomers having from 2 to 30 carbon atoms, preferably2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. Theinvention is particularly well suited to the polymerization of two ormore olefin monomers of ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the process of the invention, acopolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

In another embodiment of the process of the invention, ethylene orpropylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms. Polypropylene polymers may be produced using the particularlybridged bulky ligand metallocene-type catalysts as described in U.S.Pat. Nos. 5,296,434 and 5,278,264, both of which are herein incorporatedby reference.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, allof which are fully incorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in a gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C. Forpurposes of this patent specification and appended claims the terms“polymerization temperature” and “reactor temperature” areinterchangeable.

Other gas phase processes contemplated by the process of the inventioninclude series or multistage polymerization processes. Also gas phaseprocesses contemplated by the invention include those described in U.S.Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publicationsEP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634 421 all ofwhich are herein fully incorporated by reference.

In a preferred embodiment, the reactor utilized in the present inventionis capable and the process of the invention is producing greater than500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), evenmore preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still morepreferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even morepreferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferablygreater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr(45,500 Kg/hr).

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

A preferred polymerization technique of the invention is referred to asa particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484, which isherein fully incorporated by reference.

In an embodiment the reactor used in the slurry process of the inventionis capable of and the process of the invention is producing greater than2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr(4540 Kg/hr). In another embodiment the slurry reactor used in theprocess of the invention is producing greater than 15,000 lbs of polymerper hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998 and 5,589,555, which are fullyincorporated herein by reference

A preferred process of the invention is where the process, preferably aslurry or gas phase process is operated in the presence of a bulkyligand metallocene-type catalyst system of the invention and in theabsence of or essentially free of any scavengers, such astriethylaluminum, trimethylaluminum, tri-isobutylaluminum andtri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and thelike. This preferred process is described in PCT publication WO 96/08520and U.S. Pat. No. 5,712,352 and 5,763,543, which are herein fullyincorporated by reference.

Polymer Product of the Invention

The polymers produced by the process of the invention can be used in awide variety of products and end-use applications. The polymers producedby the process of the invention include linear low density polyethylene,elastomers, plastomers, high density polyethylenes, low densitypolyethylenes, polypropylene and polypropylene copolymers.

The polymers, typically ethylene based polymers, have a density in therange of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/ccto 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

The polymers produced by the process of the invention typically have amolecular weight distribution, a weight average molecular weight tonumber average molecular weight (M_(w)/M_(n)) of greater than 1.5 toabout 30, particularly greater than 2 to about 10, more preferablygreater than about 2.2 to less than about 8, and most preferably from2.5 to 8.

Also, the polymers of the invention typically have a narrow compositiondistribution as measured by Composition Distribution Breadth Index(CDBI). Further details of determining the CDBI of a copolymer are knownto those skilled in the art. See, for example, PCT Patent Application WO93/03093, published Feb. 18, 1993, which is fully incorporated herein byreference.

The bulky ligand metallocene-type catalyzed polymers of the invention inone embodiment have CDBI's generally in the range of greater than 50% to100%, preferably 99%, preferably in the range of 55% to 85%, and morepreferably 60% to 80%, even more preferably greater than 60%, still evenmore preferably greater than 65%.

In another embodiment, polymers produced using a bulky ligandmetallocene-type catalyst system of the invention have a CDBI less than50%, more preferably less than 40%, and most preferably less than 30%.

The polymers of the present invention in one embodiment have a meltindex (MI) or (I₂) as measured by ASTM-D-1238-E in the range from 0.01dg/min to 1000 dg/min, more preferably from about 0.01 dg/min to about100 dg/min, even more preferably from about 0.1 dg/min to about 50dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.

The polymers of the invention in an embodiment have a melt index ratio(I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from 10 to less than 25,more preferably from about 15 to less than 25.

The polymers of the invention in a preferred embodiment have a meltindex ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 25, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

In yet another embodiment, propylene based polymers are produced in theprocess of the invention. These polymers include atactic polypropylene,isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene.Other propylene polymers include propylene block or impact copolymers.Propylene polymers of these types are well known in the art see forexample U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and5,459,117, all of which are herein incorporated by reference.

The polymers of the invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes produced via conventional Ziegler-Natta and/orbulky ligand metallocene-type catalysis, elastomers, plastomers, highpressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

Polymers produced by the process of the invention and blends thereof areuseful in such forming operations as film, sheet, and fiber extrusionand co-extrusion as well as blow molding, injection molding and rotarymolding. Films include blown or cast films formed by coextrusion or bylamination useful as shrink film, cling film, stretch film, sealingfilms, oriented films, snack packaging, heavy duty bags, grocery sacks,baked and frozen food packaging, medical packaging, industrial liners,membranes, etc. in food-contact and non-food contact applications.Fibers include melt spinning, solution spinning and melt blown fiberoperations for use in woven or non-woven form to make filters, diaperfabrics, medical garments, geotextiles, etc. Extruded articles includemedical tubing, wire and cable coatings, geomembranes, and pond liners.Molded articles include single and multi-layered constructions in theform of bottles, tanks, large hollow articles, rigid food containers andtoys, etc.

EXAMPLES

In order to provide a better understanding of the present inventionincluding representative advantages thereof, the following examples areoffered.

The polymerization catalyst used in the examples below was preparedsimilarly to the following preparation. The bridged, bulky ligandmetallocene-type catalyst compound wasdimethylsilyl-bis(tetrahydroindenyl)zirconium dichloride(Me₂Si(H₄Ind)₂ZrCl₂) available from Albemarle Corporation, Baton Rouge,La. The (Me₂Si(H₄Ind)₂ZrCl₂) catalyst compound was supported onCrosfield ES-70 grade silica dehydrated at 600° C. having approximately1.0 weight percent water Loss on Ignition (LOI). LOI is measured bydetermining the weight loss of the support material which has beenheated and held at a temperature of about 1000° C. for about 22 hours.The Crosfield ES-70 grade silica has an average particle size of 40microns and is available from Crosfield Limited, Warrington, England.

The first step in the manufacture of the supported bulky ligandmetallocene-type catalyst above involves forming a precursor solution.460 lbs (209 kg) of sparged and dried toluene is added to an agitatedreactor after which 1060 lbs (482 kg) of a 30 weight percentmethylaluminoxane (MAO) in toluene (available from Albemarle, BatonRouge, La.) is added. 947 lbs (430 kg) of a 2 weight percent toluenesolution of a dimethylsilyl-bis(tetrahydroindenyl) zirconium dichloridecatalyst compound and 600 lbs (272 kg) of additional toluene areintroduced into the reactor. The precursor solution is then stirred at80° F. to 100° F. (26.7° C. to 37.8° C.) for one hour.

While stirring the above precursor solution, 850 lbs (386 kg) of 600° C.Crosfield dehydrated silica carrier is added slowly to the precursorsolution and the mixture agitated for 30 min. at 80° F. to 100° F. (26.7to 37.8° C.). At the end of the 30 min. agitation of the mixture, 240lbs (109 kg) of a 10 weight percent toluene solution of AS-990(N,N-bis(2-hydroxylethyl) octadecylamine ((C₁₈H₃₇N(CH₂CH₂OH)₂) availableas Kemamine AS-990 from Witco Corporation, Memphis, Tenn., is addedtogether with an additional 110 lbs (50 kg) of a toluene rinse and thereactor contents then is mixed for 30 min. while heating to 175° F. (79°C.). After 30 min. vacuum is applied and the polymerization catalystmixture dried at 175° F. (79° C.) for about 15 hours to a free flowingpowder. The final polymerization catalyst weight was 1200 lbs (544 kg)and had a Zr wt % of 0.35 and an Al wt % of 12.0.

Examples 1 to 7

A one liter 316 SS reactor with air-operated helical stirrer and anouter steam-heated shell and a inner acetone heat-transfer shell wasdried by heating to 115° C. while purging with 500 sccm of nitrogen for30 minutes. After cooling to 90° C., it was charged with 100 g ofpolyethylene (granular Union Carbide grade DSX4810 (available from UnionCarbide Corporation, Danbury, Conn.), Cr-based, 0.948 density, I₁₀=10,unstabilized) under inert conditions and pressure/vented four times with100 psi (690 kPa) nitrogen. A solution of 100 micromoles oftri-isobutylaluminum (TIBA) was then added and the reactor sealed andpressure/vented three times with 100 psi (690 kPa) ethylene beforebringing the reactor to reactor conditions, 80° C. and 107 psi (738kPa).

A catalyst charging vessel comprising a ¼ inch (2 cm) SS tube isolatedbetween two valves and attached to a reservoir of nitrogen was chargedwith 60.7 mg supported polymerization catalyst as described above in anitrogen-filled glove box and attached to the reactor against a nitrogenpurge. The reactor was then pressurized and vented three times withethylene. The reactor was then brought to 80° C., 107 psi (738 kPa) andthe catalyst injected. After 38 minutes the temperature was ramped to100° C. during 5 minutes and held for 40 minutes. The ideal combinationof acid and base compounds for purposes of these experiments below willhave no effect on the catalyst activity at 80° C. but will substantiallyreduce catalyst activity at 100° C.

Table 1 represents the control experiments, where no acid compound orbase compound was used with the polymerization catalyst. Controls: Theseillustrate that without the acid or base, catalyst activity issubstantial at the higher temperature range, 100° C. in these examples.

TABLE 1 Rubble Uptake Uptake Uptake % rate redn @ Ex. Acid BaseActivity¹ (%) 80° C. 100° C. 100° C./80° C. 20 min 1 none none 11847 8%14.9 31.3 2.1 −11% 2 none none 10595 6% 15.1 26.4 1.8 1% 3 none none13120 9% 17.9 30.3 1.7 −6% 4 none none 12401 28% 17.9 32.3 1.8 0% 5 nonenone 12461 26% 16.2 31.5 1.9 −18% 6 none none 12461 18% 18.7 30.9 1.7−6% 7 none none 14219 15% 16.5 36.4 2.2 4% Average 12443 16% 16.7 31.31.9 −5% Standard 1110 9% 1.5 3.0 0.2 8% Deviation ¹Activity is measuredas grams of polyethylene/mmol Zr/hour/100 psi (690 kPa) ethylene

Examples 8 to 12

As in Example 1 except that 45 mg of a 1:1 mole:mole mixture of calciumcarbonate and L-malic acid was charged to the catalyst charging vesseland injected with nitrogen pressure at 20 minutes during the 80° C.segment of the run.

Table 2 illustrates the acid/base pair reproducibly limit catalystactivity at the higher temperature. Rubble is also reduced, indicatingimproved continuity.

Examples 13 and 14

As in example 8 except that the time of injection is changed from 20minutes to 10 minutes in Example 13 and 30 minutes in Example 14.Examples 13 and 14 illustrate that the acid/base combination can beadded at various times without debit in catalyst activity before thehigher temperature period is reached.

Example 15

As in Example 8 except the acid/base compounds comprises a 1:1 mole:molemixture of potassium carbonate and L-malic acid (30 mg).

TABLE 2 Rubble Uptake Uptake Uptake % rate redn @ Ex. Acid Base Activity(%) 80° C. 100° C. 100° C./80° C. 20 min 8 L-malic CaCO₃ 6474 1% 12.8010.08 0.79 18% 9 L-malic CaCO₃ 3548 3% 9.87 4.81 0.49 31% 10 L-malicCaCO₃ 4252 2% 13.07 4.75 0.36 9% 11 L-malic CaCO₃ 6676 8% 16.60 12.370.75 0% 12 L-malic CaCO₃ 6750 10% 14.81 13.65 0.92 7% 13 L-malic CaCO₃6430 4% 14.98 12.12 0.81 −21% 14 L-malic CaCO₃ 6604 6% 13.31 12.75 0.96−7% 15 L-malic K₂CO₃ 5192 5% 12.75 7.27 0.57 37% ¹Activity is measuredas grams of polyethylene/mmol Zr/hour/100 psi (690 kPa) ethylene

Example 16

As in Example 8 except that the acid/base compounds are slurried inmineral oil (10% wt./vol.) and injected with 5 mL hexane.

Example 17

As in Example 15 except that the acid/base compounds is slurried inmineral oil (10% wt./vol.) and injected with 5 mL hexane.

TABLE 3 Rubble Uptake Uptake Uptake % rate redn @ Ex Acid Base Activity(%) 80° C. 100° C. 100° C./80° C. 20 min 16 L-malic CaCO₃ 8979 5% 15.5417.68 1.14 −25% 17 L-malic K₂CO₃ 3798 3% 11.97 3.42 0.29 21% ¹Activityis measured as grams of polyethylene/mmol Zr/hour/100 psi (690 kPa)ethylene

Examples 18 and 19

As in Example 8 except the acid/base compounds are co-mixed with thepolymerization catalyst.

Example 20

As in Example 15 except the acid/base compounds are co-mixed with thepolymerization catalyst.

TABLE 4 Uptake Rubble Uptake Uptake 100° C./ Ex. Acid Base Activity (%)80° C. 100° C. 80° C. 18 L-malic CaCO₃ 9376 3% 17.04 18.94 1.11 19L-malic CaCO₃ 5614 2% 12.20 10.54 0.86 20 L-malic K₂CO₃ 2249 8% 5.853.75 0.64 ¹Activity is measured as grams of polyethylene/mmolZr/hour/100 psi (690 kPa) ethylene

Example 21

As in Examples 18 and 19 except that the acid/base compound is slurriedwith the polymerization catalyst in toluene and then evaporated to apowder.

TABLE 5 Uptake Rubble Uptake Uptake 100° C./ Ex. Acid Base Activity (%)80° C. 100° C. 80° C. 21 L-malic CaCO₃ 6317 2% 15.05 8.38 0.56 ¹Activityis measured as grams of polyethylene/mmol Zr/hour/100 psi (690 kPa)ethylene

Examples 22 and 23

As in Examples 18 and 19 except that all components are slurried inmineral oil (10% wt./vol.) and injected with 5 mL hexane.

Examples 24 and 25

As in Example 20 except that all components are slurried in mineral oil(10% wt./vol.) and injected with 5 mL hexane.

TABLE 6 Uptake Rubble Uptake Uptake 100° C./ Ex. Acid Base Activity (%)80° C. 100° C. 80° C. 22 L-malic CaCO₃ 8604 10% 17.00 15.65 0.92 23L-malic CaCO₃ 10169 2% 25.90 12.67 0.49 24 L-malic K₂CO₃ 5492 2% 15.855.32 0.34 25 L-malic K₂CO₃ 6075 3% 15.64 4.44 0.28 ¹Activity is measuredas grams of polyethylene/mmol Zr/hour/100 psi (690 kPa) ethylene

Example 26

As in Example 8 except the acid and base are not combined with eachother, rather the base is combined with the catalyst and the acid isinjected alone at 20 minutes. Example 26 illustrates separatelyinjecting the acid from the base to the reactor.

Example 27

As in Example 8 except the acid and base are not combined with eachother, rather the acid is combined with the catalyst and the base isinjected alone at 20 minutes. Example 27 illustrates separatelyinjecting the acid from the base to the reactor.

Example 28

As in Example 15 except the acid and base are not combined with eachother, rather the base is combined with the catalyst and the acid isinjected alone at 20 minutes.

Example 29

As in Example 15 except the acid and base are not combined with eachother, rather the acid is combined with the catalyst and the base isinjected alone at 20 minutes.

Example 30

As in Example 29 except the base is slurried in mineral oil (10%wt./vol.) and injected with 5 mL hexane.

Example 31

As in Example 28 except the acid is slurried in mineral oil (10%wt./vol.) and injected with 5 mL hexane.

TABLE 7 Rubble Uptake Uptake Uptake % rate redn @ Ex. Acid Base Activity(%) 80° C. 100° C. 100° C./80° C. 20 min 26 L-malic CaCO₃ 8556 2% 15.5617.79 1.14 −8% 27 L-malic CaCO₃ 9316 3% 16.01 20.45 1.28 49% 29 L-malicK₂CO₃ 4545 5% 12.58 6.01 0.48 23% 28 L-malic K₂CO₃ 6324 4% 14.35 10.430.73 0% 30 L-malic K₂CO₃ 6507 3% 15.70 7.84 0.50 −41% 31 L-malic K₂CO₃5659 4% 13.97 6.35 0.45 0% ¹Activity is measured as grams ofpolyethylene/mmol Zr/hour/100 psi (690 kPa) ethylene

Example 32

As in Example 8 except that the acid/base mixture was prepared asfollows: 6.7 g L-malic acid is dissolved in 25 mL acetone and slurriedwith 5.0 g calcium carbonate in a 100 mL round bottom flask beforerotary evaporating to a solid and drying under vacuum at 75° C.overnight. In this Example 32 and Examples 33 and 34 below, the acidcompound is bound to the base compound.

Example 33

As in Example 32 except that only 30 mg of acid/base mixture is used.

Example 34

As in Example 8 except that the acid-base mixture was prepared asfollows: 13.4 g L-malic acid is dissolved in 46 mL acetone and addedduring 1.5 hrs to a mechanically 500 mL round bottom flask containing10.0 g calcium carbonate heated to 50° C. and purged continuously withnitrogen. After the addition the material was dried at 75° C. undervacuum overnight.

Example 35 and 36

As in Example 27 but no L-malic acid was used. Examples 35 and 36illustrate that the base compound without the acid has no effect withoutthe acid.

Example 37

As in Example 8 except that 45 mg of a 1:1 mole:mole mixture of K₂CO₃and tropic acid was used in place of L-malic acid/calcium carbonate.

TABLE 8 Rub- ble Uptake Uptake Uptake % rate redn @ Ex. Acid BaseActivity¹ (%) 80° C. 100° C. 100° C./80° C. 20 min 32 L-malic CaCO₃ 38067% 13.68 4.55 0.33 −18% 33 L-malic CaCO₃ 6108 2% 15.91 7.49 0.47 −2% 34L-malic CaCO₃ 5068 5% 17.32 3.46 0.20 5% 35 none CaCO₃ 13053 23% 14.1236.20 2.56 −2% 36 none CaCO₃ 13812 12% 15.78 37.18 2.36 −2% 37 TropicK₂CO₃ 8277 2% 17.05 20.13 1.18 −8% ¹Activity is measured as grams ofpolyethylene/mmol Zr/hour/100 psi (690 kPa) ethylene

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that adifferent combination of acid and base compounds may be used during thepolymerization process depending on the product being produced. Also,two or more polymerization reactors, in series or parallel, slurryand/or gas phase may be used in which different combinations of acid andbase compounds and/or oxidants and reductants may be used. Furthermore,the combination of acid and base compounds may be utilized downstream ofthe reactor to deactivate polymer withdrawn from a polymerizationreactor. Also, two or more polymerization catalysts may be used with theacid/base and/or oxidant/reductant of the invention. For this reason,then, reference should be made solely to the appended claims forpurposes of determining the true scope of the present invention.

1. A catalyst composition comprising an olefin polymerization catalystand at least two different solid compounds, which solid compounds reactwith each other above an onset temperature to form a polymerizationcatalyst inhibitor that deactivates the olefin polymerization catalyst,at least one compound being a carboxylic acid compound and at least onebeing a carbonate or hydroxide compound wherein the compounds do notreact with each other to form a polymerization catalyst inhibitor belowsaid onset temperature, said onset temperature being greater than 5° C.above the polymerization temperature in a polymerization reactor inwhich the catalyst composition is used, the polymerization temperaturebeing in the range of from 50° C. to 120° C.
 2. The catalyst compositionof claim 1, wherein the carboxylic acid compound, carbonate, andhydroxide compound each has a melting point greater than 70° C.
 3. Thecatalyst composition of claim 1, wherein the onset temperature isgreater than 80° C.
 4. The catalyst composition of claim 1 wherein thepolymerization catalyst is supported.
 5. The catalyst composition ofclaim 1 wherein both of the two different solid compounds have a weightloss of less than 20 weight percent measured using thermogravimetricanalysis at 80° C. for 20 minutes.
 6. The catalyst composition of claim1 wherein at least one of the two different compounds has a dielectricconstant greater than
 2. 7. The catalyst composition of claim 1 whereinsaid olefin polymerization catalyst comprises at least one earlytransition metal metallocene.
 8. The catalyst composition of claim 1,wherein the mole ratio of carboxylic acid compound to carbonate orhydroxide compound is from 2:1 to 1:2.
 9. The catalyst composition ofclaim 1, wherein the carbonate or hydroxide compound is selected fromthe group consisting of potassium carbonate, calcium carbonate, sodiumcarbonate, barium carbonate, zinc carbonate hydroxide hydrate, magnesiumcarbonate hydroxide hydrate, calcium hydroxide, sodium hydroxide,magnesium hydroxide, lithium carbonate, potassium bicarbonate andaluminum hydroxide.
 10. The catalyst composition of claim 1 wherein saidpolymerization catalyst inhibitor comprises carbon dioxide.
 11. Thecatalyst composition of claim 1, wherein the carboxylic acid compound isselected from the group consisting of o-toluic acid, tropic acid,4-octyloxybenzoic acid, 4-bromophenylacetic acid, 2-phenoxybenzoic acid,3,4,5-triethoxybenzoic acid, 2,4-dimetlioxybeuzoic acid, 3-methyladipicacid, DL-malic acid, glutaric acid, ketoglutaric acid, pimelic acid,mandelic acid, 3-t-butyladipic acid and L-malic acid.
 12. The catalystcomposition of claim 1 wherein the mole ratio of the at least onecarboxylic acid compound and the at least one carbonate or hydroxidecompound is in the range of from 20 to 0.05.